JP7133661B2 - Polythiophene-based compound/carbon fiber cloth electrode for generating water-splitting oxygen and method for producing the same - Google Patents
Polythiophene-based compound/carbon fiber cloth electrode for generating water-splitting oxygen and method for producing the same Download PDFInfo
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims description 85
- 239000004917 carbon fiber Substances 0.000 title claims description 85
- 239000004744 fabric Substances 0.000 title claims description 85
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims description 85
- 229920000123 polythiophene Polymers 0.000 title claims description 61
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims description 43
- 229910052760 oxygen Inorganic materials 0.000 title claims description 43
- 239000001301 oxygen Substances 0.000 title claims description 43
- 150000001875 compounds Chemical class 0.000 title claims description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 66
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 48
- 229930192474 thiophene Natural products 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- 238000004070 electrodeposition Methods 0.000 claims description 14
- 230000007062 hydrolysis Effects 0.000 claims description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims description 12
- 238000011065 in-situ storage Methods 0.000 claims description 12
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 12
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000010306 acid treatment Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 5
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 5
- 229910000457 iridium oxide Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000010411 electrocatalyst Substances 0.000 description 3
- 229920006254 polymer film Polymers 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/02—Electrolytic coating other than with metals with organic materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Description
本発明は、半導体ポリマーによる電気触媒水分解分野に属し、具体的には、水分解酸素発生用のポリチオフェン系化合物／炭素繊維布電極及びその製造方法に関する。 TECHNICAL FIELD The present invention belongs to the field of electrocatalytic water splitting by semiconducting polymers, and more particularly, to a polythiophene-based compound/carbon fiber cloth electrode for generating oxygen by water splitting and a method for producing the same.
社会の進歩及び科学技術の発展に伴い、人々の生活レベルは大幅に向上された。それと同時に、社会発展によってもたらされたエネルギー問題もさらに目立つになった。現在、一次エネルギーは依然として大きな比重を占めている。それがもたらす環境問題や資源不足問題によって、グリーンで持続可能な新たなエネルギーの開発が着目されている。太陽エネルギー、風力エネルギーなどのクリーンエネルギーは、直接に電気エネルギーに変換できるが、それによる電気エネルギーの貯蔵及び変換に関して、更に研究する価値がある。水の電気分解によって、水を水素と酸素に分解して、電気エネルギーを化学物質に変換して貯蔵することは、上記問題を解決するための新しい道である。また、高性能の触媒は、水分解過程における活性化エネルギーを低減でき、エネルギー消耗を大幅に低減できる。 With the progress of society and the development of science and technology, people's living standards have improved greatly. At the same time, the energy problem brought about by social development has become more prominent. At present, primary energy still occupies a large proportion. The development of green and sustainable new energy is attracting attention due to the environmental problems and resource shortages that it brings. Although clean energy such as solar energy, wind energy can be directly converted into electrical energy, the storage and conversion of electrical energy thereby deserves further research. Using water electrolysis to decompose water into hydrogen and oxygen and convert electrical energy into chemical substances for storage is a new way to solve the above problems. In addition, high-performance catalysts can reduce the activation energy in the water-splitting process, greatly reducing energy consumption.
水電解反応について、一般的に２つの半反応に分けて個別に検討する。カソードでは、２個の電子の転移に係る水素発生反応が起き、アノードでは、４個の電子の転移に係る酸素発生反応が起きるため、相対的には、酸素発生反応が難しく、過電位が高い。高効率で実用的な電極触媒によって酸素発生反応の動力学過程を加速させることは、電気化学分野において、近２０年間の研究焦点であった。 Water electrolysis reactions are generally divided into two half-reactions and considered separately. At the cathode, a hydrogen-producing reaction involving the transfer of two electrons occurs, and at the anode, an oxygen-producing reaction involving the transfer of four electrons occurs, so the oxygen-producing reaction is relatively difficult and the overpotential is high. . Accelerating the kinetics of the oxygen evolution reaction with highly efficient and practical electrocatalysts has been a research focus for the last two decades in the field of electrochemistry.
現在、研究が最も広く、性能が最も優れるのは、貴金属基触媒（例えば、酸化イリジウム）であるが、このような金属基触媒は、実際の使用時に環境問題やコスト問題がある。したがって、金属を含まない高性能触媒の開発が非常に必要である。 At present, noble metal-based catalysts (for example, iridium oxide) are the most extensively researched and have the highest performance, but such metal-based catalysts have environmental problems and cost problems when actually used. Therefore, there is a great need for the development of high performance metal-free catalysts.
近年、金属を含まないフレキシブルな重合体材料を機能性触媒として酸素析出反応を含む各種の電気触媒反応に応用されることが周知されている。ポリマーは、適合なエネルギー帯構造を有するため、水分子の解離を促進できるとともに酸素析出反応において高活性を提供できる。しかし、ポリマー電極は、その電気化学安定性が依然として実際の応用における主要な障害となる。 In recent years, it is well known that metal-free, flexible polymer materials are used as functional catalysts and applied to various electrocatalytic reactions including oxygen precipitation reactions. Because the polymer has a suitable energy band structure, it can facilitate the dissociation of water molecules and provide high activity in the oxygen precipitation reaction. However, the electrochemical stability of polymer electrodes remains a major obstacle in practical applications.
このような研究に触発されて、本願発明者は、触媒活性を向上しつつ、電極の電気化学安定性を改善できる導電性ポリマーに着目した。このようなポリマー材料は、合成方法が簡単、安価で、工業製造条件も成熟であるとともに、比較的によい電気化学安定性が得られる。ポリマーによる電気触媒電極の開発は、化学工業、エネルギー等の分野に応用できるだけでなく、電気触媒材料の研究に対しても新しい視野を提供できる。 Inspired by such studies, the inventors of the present application have focused on conductive polymers that can improve the electrochemical stability of electrodes while improving catalytic activity. Such polymer materials have simple synthesis methods, low cost, mature industrial production conditions, and relatively good electrochemical stability. The development of polymer electrocatalyst electrodes can not only be applied to the chemical industry and energy fields, but also provide a new perspective for the research of electrocatalyst materials.
本願発明は、従来技術の不足に鑑みて、電気化学安定性が高くて且つ合成方法が簡単である水分解酸素発生用のポリチオフェン系化合物／炭素繊維布電極及びその製造方法を提供する。 SUMMARY OF THE INVENTION In view of the deficiencies of the prior art, the present invention provides a polythiophene-based compound/carbon fiber cloth electrode for hydrolysis oxygen generation with high electrochemical stability and a simple synthesis method, and a method for producing the same.
本願発明に係る水分解酸素発生用のポリチオフェン系化合物／炭素繊維布電極は、炭素繊維布と、当該炭素繊維布に形成されたポリチオフェン系化合物フィルムとを含む。
前記ポリチオフェン系化合物フィルムは、チオフェン系単体が電気化学析出反応によって炭素繊維布に現場重合されてなることが好ましい。
A polythiophene-based compound/carbon fiber cloth electrode for hydrolysis oxygen generation according to the present invention includes a carbon fiber cloth and a polythiophene-based compound film formed on the carbon fiber cloth.
Preferably, the polythiophene-based compound film is formed by in-situ polymerization of a thiophene-based monomer onto a carbon fiber cloth through an electrochemical deposition reaction.
前記チオフェン系単体は、チオフェン、３位に炭素原子数１－６のアルキル基が置換されたチオフェンから選ばれた少なくとも一つであることが好ましい。
前記ポリチオフェン系化合物フィルムは、厚さが２０－１００ｎｍであることが好ましい。
The thiophene-based element is preferably at least one selected from thiophene and thiophene substituted with an alkyl group having 1 to 6 carbon atoms at the 3-position.
The polythiophene-based compound film preferably has a thickness of 20-100 nm.
これによって、水分解酸素発生用のポリチオフェン系化合物／炭素繊維布電極の触媒性能が優れる。
本願発明に係る水分解酸素発生用のポリチオフェン系化合物／炭素繊維布電極の製造方法は、チオフェン系単体と、電解質としての過塩素酸リチウムとを含有するアセトニトリル溶液を調製することと、炭素繊維布を作用電極として前記アセトニトリル溶液に浸漬させ、０．５－７時間通電して、定電圧電気化学析出法によって、チオフェン系単体を炭素繊維布に現場重合させることで、炭素繊維布にポリチオフェン系化合物フィルムを形成することと、ポリチオフェン系化合物フィルムが形成された炭素繊維布を取り出してから、純水に浸漬させて、不純物を除去し、自然乾燥させることで、ポリ水分解酸素発生用のポリチオフェン系化合物／炭素繊維布電極が得られることと、を含む。
Accordingly, the catalytic performance of the polythiophene-based compound/carbon fiber cloth electrode for generating oxygen by hydrolysis is excellent.
A method for producing a polythiophene-based compound/carbon fiber cloth electrode for generating water-splitting oxygen according to the present invention comprises preparing an acetonitrile solution containing a thiophene-based simple substance and lithium perchlorate as an electrolyte; is immersed in the acetonitrile solution as a working electrode, current is applied for 0.5 to 7 hours, and the thiophene-based simple substance is polymerized in situ on the carbon fiber cloth by a constant voltage electrochemical deposition method, so that the carbon fiber cloth is coated with a polythiophene-based compound. Forming a film, taking out the carbon fiber cloth on which the polythiophene-based compound film is formed, immersing it in pure water to remove impurities, and drying it naturally, yielding a polythiophene-based polythiophene-based compound for polyhydrolysis oxygen generation A compound/carbon fiber cloth electrode is obtained.
本願発明の製造方法によれば、均一のポリマーフィルムを形成でき、さらに、ポリマー電極に高い触媒活性を持たせることができる。
水分解酸素発生用のポリチオフェン系化合物／炭素繊維布電極の製造方法において、１ｍｏｌ／Ｌ－２ｍｏｌ／Ｌの硝酸で炭素繊維布に対して５－１０分間超音波処理を行うことを含むことが好ましい。
According to the manufacturing method of the present invention, a uniform polymer film can be formed, and the polymer electrode can have high catalytic activity.
Preferably, in the method for producing a polythiophene-based compound/carbon fiber cloth electrode for hydrolysis oxygen generation, the carbon fiber cloth is subjected to ultrasonic treatment with 1 mol/L-2 mol/L nitric acid for 5-10 minutes. .
それによって、硝酸処理後に、炭素布にポリマーをより均一に成膜できる。
前記水分解酸素発生用のポリチオフェン系化合物／炭素繊維布電極の製造方法において、前記アセトニトリル溶液は、過塩素酸リチウムの濃度が０．１－０．２ｍｏｌ／Ｌであり、前記チオフェン系単体の濃度が０．００５－０．０１ｍｏｌ／Ｌであることが好ましい。
Thereby, the polymer can be deposited more uniformly on the carbon cloth after the nitric acid treatment.
In the method for producing a polythiophene-based compound/carbon fiber cloth electrode for generating water-splitting oxygen, the acetonitrile solution has a lithium perchlorate concentration of 0.1-0.2 mol/L, and the concentration of the thiophene-based simple substance is is preferably 0.005-0.01 mol/L.
これによって、触媒性能を確保できると同時に、ポリマーフィルムが炭素布から抜けることを防止できる。
前記水分解酸素発生用のポリチオフェン系化合物／炭素繊維布電極の製造方法において、前記定電圧電気化学析出は、３時間通電することが好ましい。
As a result, the catalyst performance can be ensured, and at the same time, the polymer film can be prevented from falling out of the carbon cloth.
In the method for producing a polythiophene-based compound/carbon fiber cloth electrode for generating water-splitting oxygen, it is preferable that the constant-voltage electrochemical deposition is conducted for 3 hours.
これによって、優れる触媒性能が得られる。
前記水分解酸素発生用のポリチオフェン系化合物／炭素繊維布電極の製造方法において、前記チオフェン系単体は、炭素繊維布の表面で直接に現場重合されることが好ましい。
This results in excellent catalytic performance.
In the method for producing a polythiophene-based compound/carbon fiber cloth electrode for generating water-splitting oxygen, it is preferable that the thiophene-based monomer is directly polymerized in situ on the surface of the carbon fiber cloth.
本願発明は、水分解酸素発生における陽極としての上記電極の使用に関する。
前記ポリチオフェン系化合物は、触媒酸素析出反応の過程において制御可能な酸化反応が発生することで、触媒性能がよりよく且つより安定的なポリチオフェンを形成できる。
The present invention relates to the use of such electrodes as anodes in water-splitting oxygen generation.
The polythiophene-based compound undergoes a controllable oxidation reaction during the catalytic oxygen precipitation reaction, thereby forming a polythiophene with better catalytic performance and more stability.
本発明の水分解酸素発生用のポリチオフェン／炭素繊維布電は、活性が高く、且つ安定性がよく、水分解による酸素発生において陽極として使用でき、形状自由度が高く、水分解システムの小型化に有利であり、且つコストが低い、大規模製造に適合できる。 The polythiophene/carbon fiber cloth for water-splitting oxygen generation of the present invention has high activity and good stability, can be used as an anode in oxygen generation by water-splitting, has a high degree of freedom in shape, and can be used to reduce the size of the water-splitting system. and is low cost and amenable to large scale manufacturing.
本発明の水分解酸素発生用のポリチオフェン／炭素繊維布電極の製造方法は、プロセスが簡単で、制御しやすく、コストが低く、規模化生産を実現できる。 The method for producing the polythiophene/carbon fiber cloth electrode for water-splitting oxygen generation of the present invention is simple in process, easy to control, low in cost, and capable of being scaled up.
本願発明の水分解酸素発生用のポリチオフェン系化合物／炭素繊維布電極の製造方法は、以下のステップを提供する。
まず、チオフェン類単体と電解質としての過塩素酸リチウムとをアセトニトリルに溶解してアセトニトリル溶液を調製する。本願発明の実施例において、使用されるチオフェン系単体は、チオフェン、３位に炭素原子数１－６のアルキル基が置換されたチオフェンから選ばれた少なくとも一つである。アセトニトリル溶液は、過塩素酸リチウムの濃度が０．１－０．２ｍｏｌ／Ｌであり、チオフェン系単体の濃度が０．００５－０．０１ｍｏｌ／Ｌである。
The method for producing a polythiophene-based compound/carbon fiber cloth electrode for generating water-splitting oxygen according to the present invention provides the following steps.
First, an acetonitrile solution is prepared by dissolving a thiophene simple substance and lithium perchlorate as an electrolyte in acetonitrile. In the embodiments of the present invention, the thiophene-based monomer used is at least one selected from thiophene and thiophene substituted with an alkyl group having 1-6 carbon atoms at the 3-position. The acetonitrile solution has a lithium perchlorate concentration of 0.1-0.2 mol/L and a thiophene-based monomer concentration of 0.005-0.01 mol/L.
炭素繊維布を硝酸で超音波処理する。適当面積の炭素繊維布を前記アセトニトリル溶液に浸漬させ、炭素繊維布を作用電極として、定電圧電気化学析出法によって、チオフェン系単体を炭素繊維布に現場重合させることで、炭素繊維布にポリチオフェン系化合物フィルムを形成する。そして、電気析出完成後、作用電極を取り出して、純水に浸漬させ、不純物を除去し、自然乾燥させることで、ポリ水分解酸素発生用のポリチオフェン系化合物／炭素繊維布電極が得られる。 Sonicate the carbon fiber cloth with nitric acid. A suitable area of the carbon fiber cloth is immersed in the acetonitrile solution, and the carbon fiber cloth is used as a working electrode, and the thiophene-based monomer is polymerized in situ on the carbon fiber cloth by a constant voltage electrochemical deposition method, thereby forming a polythiophene-based compound on the carbon fiber cloth. Form a compound film. After completion of the electrodeposition, the working electrode is taken out, immersed in pure water to remove impurities, and dried naturally to obtain a polythiophene-based compound/carbon fiber cloth electrode for polyhydrolysis oxygen generation.
必要のフィルム厚さに応じて定電圧電気化学析出の通電時間を制御できるが、フィルムの厚さは２０－１００ｎｍであることが好ましく、通電時間は、０．５－７時間の範囲であることが好ましく、３時間であることがより好ましい。作用電極の純水への浸漬時間はフィルムの厚さに依存するが、例えば３０分間浸漬する。超音波処理の時間は例えば５－１０分間であり、硝酸濃度は例えば１ｍｏｌ／Ｌ－２ｍｏｌ／Ｌである。炭素繊維布は各種の規格の炭素繊維布であってもよい。前記炭素繊維布の面積は、任意の面積でよいが、必要に応じて小片に切断して使用する。本発明に使用するチオフェン類単体、過塩素酸リチウム、アセトニトリルは、すべて市販の通用製品を使用できる。 The energization time of constant voltage electrochemical deposition can be controlled according to the required film thickness, preferably the film thickness is 20-100 nm, and the energization time is in the range of 0.5-7 hours. is preferred, and 3 hours is more preferred. The immersion time of the working electrode in pure water depends on the thickness of the film, but is immersed for, for example, 30 minutes. The ultrasonic treatment time is for example 5-10 minutes and the nitric acid concentration is for example 1 mol/L-2 mol/L. The carbon fiber cloth may be carbon fiber cloth of various standards. The area of the carbon fiber cloth may be any area, but if necessary, it is cut into small pieces for use. The thiophenes simple substance, lithium perchlorate, and acetonitrile used in the present invention can all be commercially available products.
実施例１：
０．５ｃｍ×０．５ｃｍ炭素繊維布を１ｍｏｌ／Ｌの硝酸で５分間超音波処理してから、アルコールと水で超音波洗浄して用意した。０．１ｍｏｌ／Ｌの過塩素酸リチウムと０．００５ｍｏｌ／Ｌのチオフェン単体を含むアセトニトリル溶液に、上記硝酸処理後の炭素繊維布を作動電極とし、チタンネットと飽和甘汞電極をそれぞれ対極と参照電極として、三電極システムを構成した。そして、１．７３Ｖの外部電圧で３時間の定電流析出を行うことで、チオフェン単体を炭素繊維布に現場重合させ、ポリチオフェンフィルムを形成した。電気析出プロセスの完了後に、作用電極を取り出して純水に３０分間浸漬させ、不純物を除去し、自然乾燥させることで、ポリチオフェンフィルムの厚さが４０ｎｍである水分解酸素発生用のポリチオフェン系化合物／炭素繊維布電極が得られた。標準水素電極に対して１．７Ｖの電圧で測定して得られたポリチオフェン／炭素繊維布分解水酸素生成電極の電流密度は２０ｍＡ／ｃｍ－２であった。
Example 1:
A 0.5 cm×0.5 cm carbon fiber cloth was prepared by sonicating with 1 mol/L nitric acid for 5 minutes and then ultrasonically cleaning with alcohol and water. In an acetonitrile solution containing 0.1 mol/L lithium perchlorate and 0.005 mol/L thiophene simple substance, the carbon fiber cloth after nitric acid treatment is used as the working electrode, and a titanium net and a saturated calomel electrode are used as counter electrodes. As electrodes, a three-electrode system was configured. Then, galvanostatic deposition was performed at an external voltage of 1.73 V for 3 hours to polymerize the thiophene simple substance on the carbon fiber cloth in situ to form a polythiophene film. After completion of the electrodeposition process, the working electrode was taken out and immersed in pure water for 30 minutes to remove impurities, followed by air drying to obtain a polythiophene-based compound/ A carbon fiber cloth electrode was obtained. The resulting current density of the polythiophene/carbon fiber cloth decomposed water oxygen generating electrode measured at a voltage of 1.7 V against a standard hydrogen electrode was 20 mA/cm −2 .
実施例２：
０．５ｃｍ×０．５ｃｍ炭素繊維布を１ｍｏｌ／Ｌの硝酸で５分間超音波処理してから、アルコールと水で超音波洗浄して用意した。０．１ｍｏｌ／Ｌの過塩素酸リチウムと０．００５ｍｏｌ／Ｌのチオフェン単体を含むアセトニトリル溶液に、上記硝酸処理後の炭素繊維布を作動電極とし、チタンネットと飽和甘汞電極をそれぞれ対極と参照電極として、三電極システムを構成した。そして、１．７３Ｖの外部電圧で０．５時間の定電流析出を行うことで、チオフェン単体を炭素繊維布に現場重合させ、ポリチオフェンフィルムを形成した。電気析出プロセスの完了後に、作用電極を取り出して純水に３０分間浸漬させ、不純物を除去し、自然乾燥させることで、ポリチオフェンフィルムの厚さが２０ｎｍである水分解酸素発生用のポリチオフェン系化合物／炭素繊維布電極が得られた。標準水素電極に対して１．７Ｖの電圧で測定して得られたポリチオフェン／炭素繊維布分解水酸素生成電極の電流密度は６．４ｍＡ／ｃｍ－２であった。
Example 2:
A 0.5 cm×0.5 cm carbon fiber cloth was prepared by sonicating with 1 mol/L nitric acid for 5 minutes and then ultrasonically cleaning with alcohol and water. In an acetonitrile solution containing 0.1 mol/L lithium perchlorate and 0.005 mol/L thiophene simple substance, the carbon fiber cloth after nitric acid treatment is used as the working electrode, and a titanium net and a saturated calomel electrode are used as counter electrodes. As electrodes, a three-electrode system was configured. Then, the thiophene simple substance was polymerized in situ on the carbon fiber cloth by galvanostatic deposition at an external voltage of 1.73 V for 0.5 hours to form a polythiophene film. After completion of the electrodeposition process, the working electrode was taken out and immersed in pure water for 30 minutes to remove impurities and dried naturally to obtain a polythiophene-based compound/ A carbon fiber cloth electrode was obtained. The resulting current density of the polythiophene/carbon fiber cloth-decomposed water oxygen generating electrode measured at a voltage of 1.7 V against a standard hydrogen electrode was 6.4 mA/cm −2 .
実施例３：
０．５ｃｍ×０．５ｃｍ炭素繊維布を１ｍｏｌ／Ｌの硝酸で５分間超音波処理してから、アルコールと水で超音波洗浄して用意した。０．１ｍｏｌ／Ｌの過塩素酸リチウムと０．００５ｍｏｌ／Ｌのチオフェン単体を含むアセトニトリル溶液に、上記硝酸処理後の炭素繊維布を作動電極とし、チタンネットと飽和甘汞電極をそれぞれ対極と参照電極として、三電極システムを構成した。そして、１．７３Ｖの外部電圧で１時間の定電流析出を行うことで、チオフェン単体を炭素繊維布に現場重合させ、ポリチオフェンフィルムを形成した。電気析出プロセスの完了後に、作用電極を取り出して純水に３０分間浸漬させ、不純物を除去し、自然乾燥させることで、水分解酸素発生用のポリチオフェン系化合物／炭素繊維布電極が得られた。標準水素電極に対して１．７Ｖの電圧で測定して得られたポリチオフェン／炭素繊維布分解水酸素生成電極の電流密度は１２．９ｍＡ／ｃｍ－２であった。
Example 3:
A 0.5 cm×0.5 cm carbon fiber cloth was prepared by sonicating with 1 mol/L nitric acid for 5 minutes and then ultrasonically cleaning with alcohol and water. In an acetonitrile solution containing 0.1 mol/L lithium perchlorate and 0.005 mol/L thiophene simple substance, the carbon fiber cloth after nitric acid treatment is used as the working electrode, and a titanium net and a saturated calomel electrode are used as counter electrodes. As electrodes, a three-electrode system was configured. Then, galvanostatic deposition was performed at an external voltage of 1.73 V for 1 hour to polymerize the thiophene monomer on the carbon fiber cloth in situ to form a polythiophene film. After completion of the electrodeposition process, the working electrode was taken out and immersed in pure water for 30 minutes to remove impurities and air-dried to obtain a polythiophene-based compound/carbon fiber cloth electrode for hydrolysis oxygen generation. The resulting current density of the polythiophene/carbon fiber cloth-decomposed water oxygen generating electrode measured at a voltage of 1.7 V against a standard hydrogen electrode was 12.9 mA/cm −2 .
実施例４：
０．５ｃｍ×０．５ｃｍ炭素繊維布を１ｍｏｌ／Ｌの硝酸で５分間超音波処理してから、アルコールと水で超音波洗浄して用意した。０．１ｍｏｌ／Ｌの過塩素酸リチウムと０．００５ｍｏｌ／Ｌのチオフェン単体を含むアセトニトリル溶液に、上記硝酸処理後の炭素繊維布を作動電極とし、チタンネットと飽和甘汞電極をそれぞれ対極と参照電極として、三電極システムを構成した。そして、１．７３Ｖの外部電圧で５時間の定電流析出を行うことで、チオフェン単体を炭素繊維布に現場重合させ、ポリチオフェンフィルムを形成した。電気析出プロセスの完了後に、作用電極を取り出して純水に３０分間浸漬させ、不純物を除去し、自然乾燥させることで、ポリチオフェンフィルムの厚さが１００ｎｍである水分解酸素発生用のポリチオフェン系化合物／炭素繊維布電極が得られた。標準水素電極に対して１．７Ｖの電圧で測定して得られたポリチオフェン／炭素繊維布分解水酸素生成電極の電流密度は５．１ｍＡ／ｃｍ－２であった。
Example 4:
A 0.5 cm×0.5 cm carbon fiber cloth was prepared by sonicating with 1 mol/L nitric acid for 5 minutes and then ultrasonically cleaning with alcohol and water. In an acetonitrile solution containing 0.1 mol/L lithium perchlorate and 0.005 mol/L thiophene simple substance, the carbon fiber cloth after nitric acid treatment is used as the working electrode, and a titanium net and a saturated calomel electrode are used as counter electrodes. As electrodes, a three-electrode system was configured. Then, galvanostatic deposition was carried out at an external voltage of 1.73 V for 5 hours to polymerize the thiophene monomer on the carbon fiber cloth in situ to form a polythiophene film. After completion of the electrodeposition process, the working electrode was taken out and immersed in pure water for 30 minutes to remove impurities and dried naturally to obtain a polythiophene-based compound/ A carbon fiber cloth electrode was obtained. The resulting current density of the polythiophene/carbon fiber cloth decomposed water oxygen generating electrode measured at a voltage of 1.7 V against a standard hydrogen electrode was 5.1 mA/cm −2 .
実施例５：
０．５ｃｍ×０．５ｃｍ炭素繊維布を１ｍｏｌ／Ｌの硝酸で５分間超音波処理してから、アルコールと水で超音波洗浄して用意した。０．１ｍｏｌ／Ｌの過塩素酸リチウムと０．００５Ｍのチオフェン単体を含むアセトニトリル溶液に、上記硝酸処理後の炭素繊維布を作動電極とし、チタンネットと飽和甘汞電極をそれぞれ対極と参照電極として、三電極システムを構成した。そして、１．７３Ｖの外部電圧で７時間の定電流析出を行うことで、チオフェン単体を炭素繊維布に現場重合させ、ポリチオフェンフィルムを形成した。電気析出プロセスの完了後に、作用電極を取り出して純水に３０分間浸漬させ、不純物を除去し、自然乾燥させることで、水分解酸素発生用のポリチオフェン系化合物／炭素繊維布電極が得られた。標準水素電極に対して１．７Ｖの電圧で測定して得られたポリチオフェン／炭素繊維布分解水酸素生成電極の電流密度は４．８ｍＡ／ｃｍ－２であった。
Example 5:
A 0.5 cm×0.5 cm carbon fiber cloth was prepared by sonicating with 1 mol/L nitric acid for 5 minutes and then ultrasonically cleaning with alcohol and water. In an acetonitrile solution containing 0.1 mol / L lithium perchlorate and 0.005 M thiophene simple substance, the carbon fiber cloth after the nitric acid treatment was used as the working electrode, and the titanium net and the saturated calomel electrode were used as the counter electrode and the reference electrode, respectively. , constituted a three-electrode system. Then, galvanostatic deposition was performed at an external voltage of 1.73 V for 7 hours to polymerize the thiophene monomer on the carbon fiber cloth in situ to form a polythiophene film. After completion of the electrodeposition process, the working electrode was taken out and immersed in pure water for 30 minutes to remove impurities and air-dried to obtain a polythiophene-based compound/carbon fiber cloth electrode for hydrolysis oxygen generation. The resulting current density of the polythiophene/carbon fiber cloth decomposed water oxygen generating electrode measured at a voltage of 1.7 V against a standard hydrogen electrode was 4.8 mA/cm −2 .
比較例１：商業化の酸化イリジウム／炭素繊維布電極の製造
オンラインショップで購入した商業化の酸化イリジウムナノ粒子を研磨処理し、５ｍｇ取って小サンプル管に加え、さらに０．３５ｍＬの超純水、０．７０ｍＬのエチルアルコールおよび０．０８ｍＬの５％ナフィオン溶液を入れ、超音波でインクを形成した。当該インクを０．２ｍＬ取って１ｃｍｘ１ｃｍの炭素繊維布に滴下し、自然乾燥させることで、商業化の酸化イリジウム／炭素繊維布電極を得た。比較例１は、従来にてよく使用されている商業化の貴金属酸化物を使用して電極を製造したもので、実施例と性能比較を行った。
Comparative Example 1: Production of commercial iridium oxide/carbon fiber cloth electrode Commercial iridium oxide nanoparticles purchased from online shops were polished, 5 mg was added to a small sample tube, and 0.35 mL of ultrapure water was added. , 0.70 mL of ethyl alcohol and 0.08 mL of 5% Nafion solution were added and ultrasonically formed to form an ink. Take 0.2 mL of the ink, drop it on a 1 cm×1 cm carbon fiber cloth, and let it air dry to obtain a commercial iridium oxide/carbon fiber cloth electrode. In Comparative Example 1, an electrode was produced using a commercially available noble metal oxide that has been often used in the past, and the performance was compared with Examples.
以下では、製造例、特に実施例１で得られたポリチオフェン系化合物／炭素繊維布について観察して評価した。
図１は、実施例１における水分解酸素発生用のポリチオフェン／炭素繊維布電極のデジタル写真である。図２は、実施例１で得られた水分解酸素発生用のポリチオフェン／炭素繊維布電極の走査型電子顕微鏡写真である。図３は、実施例１で得られた水分解酸素発生用のポリチオフェン／炭素繊維布電極の透過型電子顕微鏡写真である。これらの写真から分かるように、電気化学析出法によって、非常に均一で高品質のポリマーフィルムが得られた。
In the following, the polythiophene-based compound/carbon fiber cloth obtained in the production examples, particularly Example 1, was observed and evaluated.
1 is a digital photograph of a polythiophene/carbon fiber cloth electrode for hydrolytic oxygen generation in Example 1. FIG. 2 is a scanning electron micrograph of the polythiophene/carbon fiber cloth electrode for hydrolysis oxygen generation obtained in Example 1. FIG. 3 is a transmission electron micrograph of the polythiophene/carbon fiber cloth electrode for hydrolysis oxygen generation obtained in Example 1. FIG. As can be seen from these photographs, electrochemical deposition yielded very uniform and high quality polymer films.
図４は、実施例１で得られたポリチオフェン／炭素繊維布電極と、比較例１で得られた酸化イリジウム／炭素繊維布電極とを酸素飽和０．１ＭのＫＯＨ溶液（ｐＨ＝１３．０）で測定したリニアスキャン電流－電圧グラフを示す。 FIG. 4 shows the polythiophene/carbon fiber cloth electrode obtained in Example 1 and the iridium oxide/carbon fiber cloth electrode obtained in Comparative Example 1 in an oxygen-saturated 0.1 M KOH solution (pH=13.0). shows a linear scan current-voltage graph measured at .
図５は、標準水素電極に対して１．７Ｖの印加電圧で４８時間の定電位安定性試験を行った場合の電流の経時変化を示すグラフを示し、最終電流は、初期電流に比べて顕著な減衰が見られなかった。 FIG. 5 shows a graph showing the change in current over time for a 48 hour potentiostatic stability test at an applied voltage of 1.7 V for a standard hydrogen electrode, the final current being significantly higher than the initial current. No significant attenuation was observed.
図４、図５のデータから分かるように、本願発明のポリチオフェン系化合物／炭素繊維布電極は、酸素発生電極として使用される場合、非常に高い電流密度を獲得できるばかりでなく、１０ｍＡ／ｃｍ－２の過電位がただ４３０ｍＶであった。なお、当該電極は、極めて優れる電気触媒安定性を有し、４８時間の定電圧安定性試験後も高電流密度を維持できることが確認された。 As can be seen from the data in FIGS. 4 and 5, the polythiophene-based compound/carbon fiber cloth electrode of the present invention not only achieves a very high current density when used as an oxygen generating electrode, but also achieves a current density of 10 mA/cm − The overpotential of 2 was only 430 mV. In addition, it was confirmed that the electrode has excellent electrocatalytic stability and can maintain a high current density even after a constant voltage stability test for 48 hours.
Claims (7)
チオフェン系単体と、電解質としての過塩素酸リチウムとを含有するアセトニトリル溶液を調製することと、
炭素繊維布を作用電極として前記アセトニトリル溶液に浸漬させ、０．５－７時間通電して、定電圧電気化学析出法によって、チオフェン系単体を炭素繊維布に現場重合させることで、炭素繊維布にポリチオフェン系化合物フィルムを形成することと、
ポリチオフェン系化合物フィルムが形成された炭素繊維布を取り出してから、純水に浸漬させて、不純物を除去し、自然乾燥させることで、水分解酸素発生用のポリチオフェン系化合物／炭素繊維布電極が得られることと、
を含み、
前記チオフェン系単体は、チオフェン、３位に炭素原子数１－６のアルキル基が置換されたチオフェンから選ばれた少なくとも１種であり、
前記アセトニトリル溶液において、過塩素酸リチウムの濃度が０．１－０．２ｍｏｌ／Ｌであり、前記チオフェン系単体の濃度が０．００５－０．０１ｍｏｌ／Ｌであるポリチオフェン系化合物／炭素繊維布電極の製造方法。 3. A method for producing a polythiophene-based compound/carbon fiber cloth electrode for generating water-splitting oxygen according to claim 1 or 2,
preparing an acetonitrile solution containing a thiophene-based element and lithium perchlorate as an electrolyte;
The carbon fiber cloth is immersed in the acetonitrile solution as a working electrode, energized for 0.5 to 7 hours, and the thiophene-based monomer is polymerized in situ on the carbon fiber cloth by a constant voltage electrochemical deposition method. forming a polythiophene-based compound film;
After taking out the carbon fiber cloth on which the polythiophene-based compound film was formed, it was immersed in pure water to remove impurities, and dried naturally to obtain a polythiophene-based compound/carbon fiber cloth electrode for generating oxygen by hydrolysis. to be
including
The thiophene-based monomer is at least one selected from thiophene and thiophene substituted with an alkyl group having 1 to 6 carbon atoms at the 3-position,
In the acetonitrile solution, the concentration of lithium perchlorate is 0.1-0.2 mol/L, and the concentration of the thiophene-based element is 0.005-0.01 mol/L. manufacturing method.
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| CN109369890A (en) * | 2018-08-29 | 2019-02-22 | 浙江工业大学 | A kind of poly- 3,4- ethene dioxythiophene Nanostructure Network film and the preparation method and application thereof |
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| JP2004253224A (en) | 2003-02-19 | 2004-09-09 | Junji Nakamura | Method of holding catalyst on fibrous carbon, fuel cell electrode utilizing the same, and fuel cell |
| JP2005044664A (en) | 2003-07-23 | 2005-02-17 | Toyota Central Res & Dev Lab Inc | Electrode catalyst and its manufacturing method |
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| WO2019065258A1 (en) | 2017-09-27 | 2019-04-04 | 積水化学工業株式会社 | Carbon dioxide reduction device, and porous electrode |
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